Anthraquinone dyestuffs



332132 Patented Nov. 30, 1965 3,221,020 ANTHRAQUINONE DYESTUFFS Riitger Neeif, Leverkusen, Germany, assignor to Farbenfabriken Bayer Aktiengesellschaft, Leverlrusen, Germany, a corporation of Germany No Drawing. Filed Aug. 2, 1962, Ser. No. 214,208 Claims priority, application Germany, Aug. 5, 1961,

6 Claims. (Cl. 260-303) This invention relates to new anthraquinone dyestuffs and to a process for their production.

It is an object of the present invention to provide new anthraquinone dyestuffs with excellent fastness properties. Further objects will appear hereinafter.

We have found that new and valuable vat dyestuifs are obtained if at least two mols of an anthraquinone-2- aldehyde or of a corresponding anil are condensed with one mol dithio oxamide (rubeanic acid).

Anthraquinone aldehydes or anils that can be used are especially anthraquinone-Z-aldehyde and its halogeno, amino, acylamino, alkylsulfono, arylsulfono and sulfonamido derivatives or the corresponding anils, as well as anthraquinone-Z-aldehyde to which ring structures have been joined by condensation, such as for example 1,9- thiazolanthraquinone-Z-aldehyde or its anil. Examples are: anthraquinone-Z-aldehyde and l-chloro-anthraquinone-2-aldehyde, 1-amino-anthraquinone-Z-aldehyde, its 6-chloro-; 7-chloro-; 6,7-dichloro-; 6- or 7-chloro-, fluoro-, and bromo derivatives, its 6- or 7-alkyl or arylsulfono or 6- or 7-sulfonamide derivatives or the corresponding anils.

We further mention 4- or S-acyl-amino-l-amino-anthraquinone-2-aldehydes or their anils, wherein the acyl radicals may be, for example, from the following carboxylic acids: benzoic acid, 2-, 3-, or 4-chloro-, bromo-, fiuoro-, methylor methoxy benzoic acid, 2,4- or 2,5-dichloro or 3,4-dibromo benzoic acid, benzoic acid-3 or -4-alkylsultones, benzoic acid -4-sulfonamides, cinnamic acid, diphenyl-4-carboxylic acids which may be halogeno-substituted, naphthalene carboxylic acids, and anthraquinone- Z-carboxylic acids which may be substituted with nitro or amino groups. The dyestuffs made from 4- or S-acylamino-1-amino-anthraquinOne-Z-aldehydes or their anils can also be produced by condensing 1,4- or 1,5-diaminoanthraquinone-2-aldehydes or their anils with dithio oxamide and subsequently carrying out an acylation with acid halides, for example the acid halides of the acids listed above.

Naturally, it is also possible by using a mixture of two differently substituted anthraquinone-aldehydes or their anils to produce the corersponding asymmetric dyestuifs or dyestutf mixtures. If 1-chloro-anthraquinone-2-aldehyde or its anil is used as the condensation component the chlorine atoms of the resulting dyestuif can be exchanged with amino groups by the reaction with p-toluenesulfamide and subsequent saponification. The dyestuff obtained is identical with the product obtained from l-aminoanthraquinone-2-aldehyde.

The dyestuffs are produced by heating the anthraquinone aldehydes or their anils with dithio oxamide in inert organic solvents to about 80200 C. Suitable solvents are, for example, halogenated benzene hydrocarbons such as o-dichlorobenzene; nitrobenzene; methylnaphthalene; glacial acetic acid; alcohols, such as amyl alcohol; and glycol ethers, such as ethyleneglycol-monoethylether, or their esters, for example the acetate; dimethylformamide or -sulfoxide; pyridine, alkylpyridines or mixtures thereof.

It is of special importance that it is not necessary to use the substituted free anthraquinone aldehydes which are not easilyobtainable, but the process according to the invention can be started with the corresponding aldehydeanils which can be easily produced, for example, by oxidation of the corresponding methylanthraquinones with nitrobenzene.

The obtainable anthraquinone dyestuffs are either used as such or in the form of leuco-ester salts, which are produced by known methods, for dyeing or printing animal or preferably vegetable or artificial fibres, for example wool, silk, but particularly cotton, linen, regenerated cellulose, rayon or polyamide or polyurethane fibres. Yellow, blue, grey, green and brown dyeings or prints are obtained distinguished by excellent fastness to wet processing and light as well as their resistance to water drops and their intense coloration.

The following examples are given for the purpose of illustrating the invention:

Example 1 19.5 parts 1-amino-anthraquinone-Z-aldehyde-anil and 3.6 parts dithio oxamide are heated to the boil in parts dimethylformamide Within one hour and then boiled for about 5-6 hours. The reddish-blue needles formed are filtered off with suction and, after cooling, are separated from the solvent in the usual manner. The dyestutf thus obtained crystallises in boiling nitrobenzene to reddish blue prisms, yields, when vatted, a blue-grey vat and has, according to analysis, the following constitution 0.2 g. of the dyestutf are added at 50 C. to 200 cc. of a dye liquor consisting of 1.4 cc. sodium hydroxide solution (38 B.), 0.8 g. hydrosulphite, 4 g. sodium sulphate and a suitable quantity of water. The mixture is left to vat for 15 minutes at 50 C., and then a pre-wetted cotton skein (10 g.) is dyed in the blue-grey vat for about 45 minutes at 50 C. The dye is squeezed 01f, oxidised in air, then well rinsed and acidified with a solution of 4 g. acetic acid per litre. The rinsed goods are soaped at the boil for 15 minutes, rinsed and dried in the usual manner. A reddish dark-blue colour is obtained, distinguished by very good fastness to light and wet processing and resistant to water-drops.

If for the production of this dyestuif we used instead of the above mentioned 1-amino-anthraquinone-2-aldehydeanil its 6- or 7-methy1- or ethy1sulphono-, 6- or 7-phenylsulphonoor 6- or 7-sulphonamide derivatives, which may be substituted in the amide nitrogen atom with one or two methylor ethyl groups, reddish dark-blue dyeing products with excellent fastness properties were likewise obtained.

Instead of carrying out the production of the dyestuif in dimethylformamide it can be done, with equal success, using solvents such as o-dichlorobenzene, nitrobenzene, dimet-hylsulphoxide, glacial acetic acid, ethylene-glycol, ethylene-glycol-monoethyl ether, ethylene-glycol-monomethyl ether acetate or mixtures thereof.

Example 2 22.2 parts 6-chloro-1-amino-anthraquinone-2-aldehydeanil and 3.6 parts dithio oxamide are heated to the boil in 150 parts dimethylformamide until the reaction is completed. The dyestutf, separated in the usual manner, dyes cotton from a blue-grey vat in neutral dark blue shades with very good fastness to wet processing, light and water-drops and has the following constitution Products with similar dyeing properties are obtained when using instead of 6-chloro-1-amino-anthraquinone-2-aldehyde-anil equivalent quantities of 7-chloro-, 6- or 7- chloro or 6,7-dichloro-l-amino-anthraquinone 2 aldehyde-anil or corresponding bromoor fluoro derivatives.

Example 3 20 parts anthraquinone-Z-aldehyde and 5.1 parts dithio oxamide are heated to the boil in 150 parts dimethylformamide until the dyestuff formation is completed. The crystallised dyestuff is filtered off with suction and separated from the solvent in the usual manner. The product dyes cotton from an olive coloured vat in clear yellow shades with very good fastness properties and has the following constitution:

E) C/N S\O can ll Example 4 5.5 parts anthraquinone-Z-aldehyde are transformed into the anil by heating them with 2.3 parts aniline in 150 parts dimethylformamide. 7.5 parts 1-amino-anthraquinone-Z-aldehyde-anil and 2.7 parts dithio oxamide are added and the mixture is heated to boiling point for about 4 hours. After termination of the condensation the reaction product, crystallised in the form of beautiful dark brown needles, is filtered off with suction and separated from the solvent in the usual manner. The dyestufi' dyes cotton from a blue-grey vat in brownish black shades and has the following constitution:

1 R C C i1 1 l JL m ExampleS 15 parts l-amino 4 benzoylamino-anthraquinone-2- aldehyde-anil and 1.9 parts dithio oxamide are heated to the boil for about 2 hours together with 150 parts dimethylformarnide. The blue-green product thus obtained is separated in the usual manner and dyes cotton from a blue-grey vat in bluish green shades, which possess excel- (I) 11111 S \C Hg El l l N I l I NH 7 lent fastness to light and wet processing. According to analysis, the dyestuff has the following constitution:

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Example 6 34.1 parts 1,4-diamino-anthraquinone-2-aldehyde-anil are heated to the boil together with 6 parts dithio oxamide in 300 parts dimethylformarnide until the formation of the intermediary product of the formula.

0 NH; N S HzN 0 N 0/1 \C I ll N (l r'm. 11.15 A

is terminated. If subsequently 25 parts of the intermediary product are acylated in 360 parts nitrobenzene by the addition of 19 parts 2,4-dichlorobenzoyl chloride at C. and heating the reaction mixture to -205 C.

a dyestutf of the formula fl) NH, /N]/S\ H N o o L 0 mo I I A 1'; mi 6 o m COQ-Cl 1 1 is obtained which dyes cotton from a blue-grey vat in bluish green shades with excellent fastness properties. A dyestuif with similar dyeing properties is obtained by using instead of 2,4-dichlorobenzoyl chloride an equivalent quantity of m-trifiuoromethylbenzoyl fluoride.

Example 7 To 20 parts of the intermediary product described in Example 6 in 200 parts nitrobenzene there are added at 80-100" C. 15 parts diphenyl-4-carboxylic acid chloride and the mixture is heated to -205 C. until acylation is terminated. The dyestutf obtained has the formula QQQ .5 and dyes cotton from a blue-grey vat in bluish green shades.

Example8 7.5 parts 1-amino-anthraquinone-Z-aldehyde-anil, 11

6 product, crystallised in yellow needles, is filtered off with suction, washed with methanol and dried. The dyestub. thus obtained, having the formula parts 1 amino 4 benzoylamino anthraquinone 2- 5 aldehyde-anil and 2.7 parts dithio oxamide are heated to the boil in 120 parts dimethylformamide and 20 parts 0 C glacial acetic acid until the dyestufi formation ceases to increase. The dyestuff separated in the usual manner, of S N the formula It I EI) NH: N S H21? A dyes cotton from a brown vat in clear yellow shades with C C excellent fastness to wet processing and light l H I H E l 12 S N xamp e H 5.5 parts anthraquinone-2-alde'hyde are transformed O I 0 into the corresponding anil by heating it with 2.3 parts comm aniline and 120 parts dimethylformamide. 11 parts dyes cotton from a blue-grey vat in intense marine blue 1 P 4 benzoylfmfmo anPhraqumone 2 alde' shades, distinguished by very good fastness to wet procx and dlthlojoxamlde are added and the essing, excellent fastness to light and fastness to watermlxture 1S heated 9 the boll for about 4 s hours' The drops If an equivalent quantity of dyestutf, separated in the usual manner, havmg the probthoxy benzoylamino) anthraquinone 2 aldehyde anil able formula is used instead of 1-amino-4-benzoylamino-anthraquinone- Z-aldehydeanil a slightly greenish marine blue dyestuff of O N s 0 similar dyeing properties is obtained. I T

C C Example9 I /l\ I 15 parts 1-amino-S-benzoylamino-anthraquinone-Z-als N dehyde-anil and 1.9 parts dithio oxamide are heated in Y I 120 parts nitrobenzene and 5 parts glacial acetic acid for 0 NHCO-CGHS 0 about 5 'hours to 150-l60 C. The product thus obtained is filtered oil with suction and separated from nitrodyes cotton from a blue-grey vat in yellowish green shades benzene by Washing it with methanol. The dyestufi obwhich possess excellent fastness to light and wet proctained, of the formula essing.

R IITH: /N S H21? (3 I I I I i \S N/ C5H5.CO.NH i i) I\'IH.CO.C5H

dyes cotton from a blue-grey vat in blue-black shades Example 13 with good.fastness P y f fi P' 7.7 parts anthraquinone-Z-aldehyde are transformed benzoylammo-anthraqumone 2 aldehyde anil, an equlvainto the corresponding anil by heating them with 3 2 g g ggfg g g gg gig g-gg l-g ggjg f g ggg parts aniline and 120 arts dimethylformamide. After 1 y 1 y adding 6.6 parts 1-amino-4-benzoylamino-anthraquinoneof similard em ro erties is obtained y g p p 2-aldehydean1l the mlxture is heated to the boil until dye- Example 10 stufi formation stops increasing and the dyestuff thus 7.5 parts 1-amino-4-benzoylamino-anthraquin-one-2-alg g whllch a g 9 the f q g i dehydeanil and 7.5 parts 1-amino-S-benzoylarnino-anthraun er fi as i g 2 2 i t e f quinone-Z-aldehyde-anil are heated to the boil together f E d yes co on mm a with 1.9 parts dithio oxamide in 150 parts of dimethylgrey Va m as ye 0W wens a formamide until the dyestutf formation stops increasing. Example 14 g i separated m the usual manner of the 5.5 part anthraquinone-Z-aldehyde are transformed 0mm a into the corresponding anil by heating them with 2.3 parts IITH1 NIIIT I aniline and 120 parts dimethylformamide. 11 parts AA 1 amino 5 benzoyl amino anthraquinone 2 alde- C C hyde anil are added, the mixture is heated to the boil for I about 4-5 hours and the product thus formed is sepa- S N rated. The dyestuif obtained, of the probable formula o n N s 0 0 0 P n 2 cocfln 00.05115 0 l C dyes cotton from a blue-grey vat in greenish dark-blue A y l shades distinguished by their fastness to wet processing S N and their resistance to Water-drops. I I I Example 1] 1 0 0 15 parts thiazolanthrone-Z-aldehyde-anil and 2.64 parts dithio oxamide are heated to the boil together with 120 dyes cotton from a grey vat in olive-coloured shades, disparts dimethylformamide for about 45 hours. The tinguished by their fastness to wet processing and light.

3,221,020 7 8 I claim: 4. Dyestuff of the formula 1. A dyestuff of the formula NH H N ll X C & C Y 5 S N S N u u wherein X and Y are members selected from the group 0 I 0 consisting of anthraquinonyl, thiazolanthrone and an- 00.06115 thraquinonyl substituted, when desired, by a member Dyestuff of the formula selected from the group consisting of halogen, amino-,

benzoylamino, naphthoylamino, monoha-lobenzoylamino, 5 N mono'halon-aphthoylamino, dihalobenzoylarnino, dihalonaphthoylarnino, diphenylamino, alkylbenzoylamino, 21- r kylnaphthoylamino, alkoxybenzoylamino, alkoxy naphthoylarnino, alkylsulfonbenzoylamino, alkylsulfononaph- S thoylamino, cinnamoyl amino, alkylsulfono; phenyl- II A sulfonoand sulfonamido.

2. Dyestuif of the formula Dyestuff 0f the formula [0 lTTHz N\/ S Hz (I) 3 N H2 /N\/ S (I? A G I ll| Ill lll s/ II A 0 Dyestufi of the formula References Cited by the Examiner 5 NICHOLAS S. RIZZO, Primary Examiner.

JOHN D. RANDOLPH, WALTER A. MODANCE,

Examiners.

NH 3 00mm $0.0m,

O N111 N s H2N 0 Degering: An Outline of Organic Nitrogen Compounds (Michigan, 1945 pages 491-2.

0 C Johnson et a1.: J. Am Chem. Soc., vol. 82, pages 2719- i i I 2724 (1960).

s N ii 1 H 

1. A DYESTUFF OF THE FORMULA 